CN101490164A - Thermoplastic articles and processes for making the same using an improved masterbatch - Google Patents
Thermoplastic articles and processes for making the same using an improved masterbatch Download PDFInfo
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- CN101490164A CN101490164A CNA2007800245007A CN200780024500A CN101490164A CN 101490164 A CN101490164 A CN 101490164A CN A2007800245007 A CNA2007800245007 A CN A2007800245007A CN 200780024500 A CN200780024500 A CN 200780024500A CN 101490164 A CN101490164 A CN 101490164A
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- polyolefine
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- tpo
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- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000004594 Masterbatch (MB) Substances 0.000 title description 17
- 229920001169 thermoplastic Polymers 0.000 title description 5
- 239000004416 thermosoftening plastic Substances 0.000 title description 5
- 239000000463 material Substances 0.000 claims abstract description 164
- 239000000203 mixture Substances 0.000 claims abstract description 49
- 229920000098 polyolefin Polymers 0.000 claims abstract description 44
- 239000000155 melt Substances 0.000 claims abstract description 16
- 239000012764 mineral filler Substances 0.000 claims abstract description 10
- -1 polypropylene Polymers 0.000 claims description 33
- 239000004743 Polypropylene Substances 0.000 claims description 29
- 229920001155 polypropylene Polymers 0.000 claims description 29
- 239000000945 filler Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 238000001746 injection moulding Methods 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 18
- 239000000454 talc Substances 0.000 claims description 15
- 235000012222 talc Nutrition 0.000 claims description 15
- 229910052623 talc Inorganic materials 0.000 claims description 15
- 239000006187 pill Substances 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 4
- 238000010008 shearing Methods 0.000 claims description 4
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- HZFDKBPTVOENNB-GAFUQQFSSA-N N-[(2S)-1-[2-[(2R)-2-chloro-2-fluoroacetyl]-2-[[(3S)-2-oxopyrrolidin-3-yl]methyl]hydrazinyl]-3-(1-methylcyclopropyl)-1-oxopropan-2-yl]-5-(difluoromethyl)-1,2-oxazole-3-carboxamide Chemical compound CC1(C[C@@H](C(NN(C[C@H](CCN2)C2=O)C([C@H](F)Cl)=O)=O)NC(C2=NOC(C(F)F)=C2)=O)CC1 HZFDKBPTVOENNB-GAFUQQFSSA-N 0.000 description 1
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- VSTOHTVURMFCGL-UHFFFAOYSA-N [C].O=[Si]=O Chemical compound [C].O=[Si]=O VSTOHTVURMFCGL-UHFFFAOYSA-N 0.000 description 1
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- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 229910052618 mica group Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- 235000012239 silicon dioxide Nutrition 0.000 description 1
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- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229920001866 very low density polyethylene Polymers 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
Abstract
The present invention is directed to improve processes for making plastic articles, and articles made therefrom. In a broad aspect, the invention is directed to improved processes and articles made therefrom, that include the steps of providing as separate materials a first material that includes a polyolefin, a second material including an admixture of from about 45 to 85 wt.% of the total admixture of at least one particulated mineral filler; and from about 15 to 55 wt.% of the total admixture of at least a second polyolefin having a melt index greater than about 150 g/10min at 190 DEG C/2.16kg, as measured per ISO 1133 (condition D); applying a shear force to form a molten blend; shaping the molten blend and solidifying the molten blend.
Description
Submit a day rights and interests requirement to
The application requires the submission day rights and interests of the U.S. Provisional Application series number 60/806,179 of submission on June 29th, 2006, and it is incorporated herein by this reference for various purposes.
Invention field
The present invention relates to the thermoplastic article and the manufacture method thereof of moulding, one concrete aspect in, use the injection molding polyolefin articles of improved masterbatch material blend when relating in injection moulding machine.
Background of invention
In the plastics field, need to have good mechanical properties all the time and relatively cheap material efficiently on making.Along with the cost of the nearest prices of raw and semifnished materials and the used energy of work material increases, strengthened research to the attractive equivalent material system of the physics that satisfies many existing commercial plastics and mechanical requirements.In the TPO field, for example, a kind of reduction is to prefabricated compounding step, and particularly those are attractive to dependent effective material system that starting material apply the step that thermal history and/or processing requires the expenditure of energy.
Example at the document of material preparation in this field comprises open U. S. application No.US20040048967A1,20050070673A1,20050250890A1,20050049346A1; United States Patent(USP) Nos. 4,732,926; 5,130,076; 6,403,691; With 6,441,081; European patent application No.0987091A1; Japanese patent application 2004168876; WO2004/031292A2; Verbraak, people such as C., ＂ Screw Design in Injection Molding (screw design in the injection molding) ＂ Polym.Eng.﹠amp; Sci., the 29th volume, No.7,1989, the 479-487 pages or leaves; Han, C.D., Deng the people, ＂ Morphology and Mechanical Properties of Injection MoldedSpecimens of Two-Phase Polymer Blends (form and the mechanical properties of the injection molding sample of two-phase polymer blend) ＂ Journal of Applied Polymer Science, the 21st volume, 1977, the 353-370 pages or leaves; With ＂ EXACT Plastomers-High PerformanceSolutions for TPO Applications (EXACT plastomer-be used for the efficient solution of TPO purposes) ＂ ExxonMobil Technical Bulletin, in May, 2005, all these is quoted hereby and incorporates this paper into.
Summary of the invention
The present invention relates to make plastics improve one's methods and by its goods of making.In broad aspect, the present invention relates to improved method and by its goods of making, this method comprises the following steps: to provide with the separate material form and comprises polyolefine or first material that is made of polyolefine (for example TPO) substantially and comprise particulate filler and second material of the second polyolefinic mixture; When material is under the elevated temperature, first and second materials are applied shearing force so that the material blend is formed melt blended material; With this melt blended material moulding and this melt blended material is solidified.
In aspect more specifically, this method use at least a fibrous mineral filler that accounts for about 45 to the 85 weight % of total mixture and account for about 15 to the 55 weight % of total mixture have according to ISO 1133 (condition D) record under 190 ℃/2.16 kilograms greater than at least the second polyolefinic masterbatch mixture of/10 minutes melt index of about 150 grams as second material.In addition, this method is not contained in before the blend step step that first and second materials is compounded in together substantially.
Accompanying drawing is described
Fig. 1 a and 1b are that show can be according to the exemplary microgram of the microstructure of this instruction acquisition.
Detailed Description Of The Invention
The present invention relates to make plastic products improve one's methods and by its goods of making. In broad sense The aspect the present invention relates to Innovative method and by its goods of making, the method comprises the following step Suddenly: (for example thermoplastic poly alkene, polypropylene are common to provide first polyolefin with the separate material form Poly-thing or polypropylene homo thing, its any combination or other), comprise granular filler and second poly-The masterbatch mixture of alkene (for example, accounts at least a of about 45 to 85 % by weight of total mixture Fibrous mineral filler and account for the having according to ISO 1133 of about 15 to 55 % by weight of total mixture What (condition D) recorded restrains/10 minutes melt greater than about 150 under 190 ℃/2.16 kilograms At least the second polyolefinic mixture of index) second material; Be in the rising temperature at material Under the time this material applied shearing power the material blend is formed melt blended material; Should melt Melt blend molding and this melt blended material is solidified. Desirably, the method is not contained in the blend step Before rapid first and second materials are compounded in step together, and especially do not contain and comprise that melt altogether The formerly compounding step of mixed step.
Can find out from the above, the step of this melt blended material moulding can be used many industries Any or its combination of the technology of interior disclosed manufacturing moulded products is carried out. For example, moulding can To be undertaken by blowing, injection moulding or its any combination. Generally speaking, this kind step has Use to be fit at elevated temperatures raw material be applied the device of shearing power especially sharply, thereby obtain Get melt blended material. For example, typical method is used the device with screw rod and machine tube assembly, To wherein adding raw material (for example herein first and second materials ball grain separately), for example from Reservoir vessel is directly introduced and is introduced via mixed-hopper. Along with material is assembled at screw rod and machine tube Along the screw rod feeding, it is by disperseing mixing and/or mixing by the distribution mixing method in the part. Use is stirred Mix the ball grain that blade is dry mixed first and second materials. Can use suitable feeder, for example heavy The power feeder, with or (for example be not with gravity type metering batch mixer (weigh scale blender) Can be available from Maguire).
The size of the pill of first and second materials is roughly similar each other.For example, desirably, at least 50 weight % (with more specifically, about at least 65 weight %) the first material pill and the second material pill have essentially identical size (being their longest dimensions separately in about 15% change each other).
In one embodiment of the invention, the pill of first material usually less than the pill of second material so that the average-volume of each pill of first material less than the average-volume of each pill of second material.Average-volume can also be measured this quality by the quality of measuring 100 pills of selecting at random divided by 100 times amount of density of material, wherein volume unit is a cubic centimetre, and mass unit is a gram, and density unit is a gram/cubic centimetre.
On demand, can make the material experience mix scraper plate (mixing flight), it comprises that at least one grooving that is used to provide dispersing and mixing (undercut) and/or at least one are used to provide distribution blended by-pass channel.After forming required blend, intermingling material is discharged from device, as discharging, and it is contacted with the mold wall that is used to limit required article shape by optional mixing nozzle.
The example of available processing conditions is disclosed in (but being not limited to) U.S. Provisional Patent Application series number No.60/745 according to the present invention, and among 116 (the certificate number 1062-058P1), it is incorporated herein by this reference.For example but be not limited, screw rod used herein and machine barrel assembly can have any suitable dimension that is used to realize required result.In a kind of method that blend step is therein carried out in screw rod and machine barrel assembly, this screw rod and machine barrel assembly have greater than about 5:1, and be more special in about 10:1, the more special again length-to-diameter ratio greater than about 15:1 (for example about 15:1 to 25:1).
According to the instruction of this paper, available another consideration item is to select suitable back pressure (promptly in the screw reset process to the plastics applied pressure) and/or screw compression ratio in the blend process in screw rod and machine barrel assembly.For example, in illustrative aspects, in the blend step, first, second and the 3rd material are applied about at least 6 crust, more special about at least 10 crust, or even the back pressures of about at least 25 crust (for example about 70 crust), use is greater than the screw compression ratio of about 1:1 (more special at least approximately 2:1, for example about 2:1 to 3.5:1 or higher (for example about 2.4:1)), or both combinations.Higher and lower value is also feasible.
May be desirable be, in the blend step, use about 20 to 400rpm, about more especially 50 to about 250rpm, more about more especially 100 to about 200rpm the screw speed of (for example approximately 160rpm).
The blend step can carried out under stark suitable any melt set point temperature used concrete machine.For example, it can be more in particular in about 210 to about 255 ℃ at about 160 to about 300 ℃, is more in particular in about 220 again and carries out to about 240 ℃ machine melt set point temperature.
Randomly, injecting step comprises makes blend pass through static mixer, as mixing nozzle (for example producing the mixing nozzle at interface).
Can use various disclosed in the industry screw design to realize well blend, high-performance designs is attractive especially.A feature of high-performance designs is to exist two or more to have along the passage of the channel size of spiro rod length variation.This variation of channel size is ordered about material and is flowed between passage, mixes thereby improve.For example, distribute and mix and to realize by cutting and folded polymeric thing melt-flow, and dispersing and mixing can realize by limiting channel by ordering about polymer molten fluid.Some examples of high performance screws include but not limited to, transmission ofenergy (ET) screw rod, double wave screw rod, Stratablend
TMScrew rod and UniMix
TMScrew rod.Also can use the secondary mixing equipment to mix to improve.These secondary mixing equipment can be incorporated in the screw design (dynamic mixer), or they can incorporate (static mixer) in the screw rod downstream into.Some examples of dynamic mixer include but not limited to, one or more in Maddock type mixing tank, bubble-cap mixing tank (blister mixers), spiral dam (spiral dam) mixing tank, pin mixer (pin mixer) and the hybrid ring.Some examples of static mixer include but not limited to Kenics
TMMixing tank, interface producer (interfacial surface generator (ISG)) mixing tank and Koch
TMMixing tank.Under injection molding situation, this class static mixer designs can be incorporated in the nozzle and they are known as mixing nozzle.
From above as can be seen, comprise that melt blended raw-material compounding method, desirable especially method are to omit this step although can choose wantonly to use before with the material feeder.Therefore, this method is not contained in before the blend step step that first and second materials is compounded in together substantially.
For first material, usually, it comprises polyolefine, (for example more especially comprise two or more alpha-olefin comonomer, propylene, 1-butylene, 1-hexene, 1-octene) thermoplastic elastomer, or TPO (promptly comprising polypropylene and toughness reinforcing component) more especially as the polyolefin alloy of ethylene-propylene copolymer.Desirably, first used in the method for this paper material comprises the polypropylene impact copolymer with following feature: less than/10 minutes (ISO 1133 condition M of about 70 grams, 230 ℃, 2.16 kilogram) (for example, about 1 to about 55 restrains/10 minutes, about more especially 3 to about 45 the gram/10 minutes, about more especially again 4 the gram/10 minutes to about 20 the gram/10 minutes) melt flow rate (MFR); Contain ethene greater than about 8 weight % (by the weight of first material) (for example, greater than about 12 weight % ethene); Degree of crystallinity is greater than about 30% (for example, greater than about 50%), has less than about-30 ℃ second-order transition temperature with less than the density of about 0.92 gram/cubic centimetre, or their any combination.As the optional rubber that does not contain divinyl substantially of the material of first material, as SBS or SBR rubber.The example of the first suitable material can be used as research and development (developmental) acrylic resin and runs after fame available from The DowChemical Company with Developmental Polypropylene Resin DC7003.00.Another example of the first suitable material can be used as D143.00 research and development TPO available from The Dow Chemical Company, and manufacturers is described as high-impact reactor TPO level with it.
First polyolefine preferably comprises the TPO that is selected from reactor TPO, controlled rheology TPO or its combination.
In final total material, first material usually with final material greater than about 20 weight %, more special in about 35 weight %, the amount of about more especially 40 to about 98 weight % (about more especially 75 to about 95 weight % again) exists.Can use the replacement of homopolymer polypropylene or atactic polypropylene copolymer or replenish polypropylene impact copolymer.Recognize that the polymkeric substance of its pure state can be desirably used in the use of the polymkeric substance of this paper.Certainly, this instruction also expects may comprising in this polymkeric substance suitable disclosed in the industry additive types, as finings/nucleator, lubricant, surface slip agent, stablizer (as thermo-stabilizer), its any combination or similar type.
And for second material, it generally includes masterbatch mixture of the present invention, described masterbatch mixture comprise or (in aspect more specifically) substantially by the particulate filler and second thermoplastic material, particularly second polyolefine constitutes.Although can use the alternative filler (for example mica, lime carbonate, silicon-dioxide, clay, timber, titanium dioxide) openly in the industry of any kind, preferred filler is that talcum is (for example substantially by 3MgO4SiO
2H
2The talcum that O constitutes).This filler can have any suitable median particle, for example, about 10 microns or littler (for example, about 7 microns or littler, or even about 5 microns or littler, or may in addition less than about 3 microns (for example, less than about 1 microns)) the order of magnitude.This filler can be any suitable overall dimension (top-size) granularity, the order of magnitude of for example about 50 microns or littler (for example, less than about 30 microns, or more special in about 15 microns).
For second material, desirably, filler in advance with the second thermoplastic material compounding (for example by melt blended step).The compounding or the melt blended step that are used to prepare second material can adopt, but are not limited to single screw extrusion machine, twin screw extruder or kneader.Filler desirably mixes so that it is evenly distributed in whole second material usually.At this moment, also can mix second material to comprise one or more additives as other local instruction of this paper.Also can or after this add tinting material or pigment in this stage.In one approach, except that second polyolefine, also available another polymkeric substance that desirably adds, as polyethylene (for example LLDPE), homopolymer polypropylene, or some other compatible materials are to regulate the performance characteristic of gained material.Therefore, as can be seen, second material can use the polymkeric substance with the first material same type, or another polymkeric substance, or the combination of polymkeric substance.
Desirably, the enough low consequently gained viscosity of masterbatch mixture of the viscosity of second material (viscosity is measured down in melt condition (for example, under about 177 ℃ order of magnitude, according to ASTM D1084)) will be lower than polyolefinic viscosity in first material.
In a specific examples according to this instruction, second polyolefine is a polyolefin plastomers, and particularly the melt index under 190 ℃/2.16 kilograms that records according to ISO 1133 (condition D) is greater than the polyolefin plastomers of about 150 grams/10 minutes (more special greater than about 250 or even 500 grams/10 minutes).It is about at least 80% that this class material desirably shows, more special about at least 100% ultimate elongation (according to ASTMD 638); At least about 145psi (1MPa), the more special at least approximately tensile strength (according to ASTMD638) of 200psi (1.3MPa).The specific examples of suitable polyolefin plastomers can be run after fame available from The Dow Chemical Company with AFFINITY GA 1900 and AFFINITY GA 1950.
In a specific examples according to this instruction, second polyolefine is a propylene-ethylene copolymers, and particularly the melt index under 230 ℃/2.16 kilograms that records according to ISO 1133 (condition M) is greater than the propylene-ethylene copolymers of about 10 grams/10 minutes (more special greater than about 16 or even 20 grams/10 minutes).It is about at least 35% that this class material desirably shows, more special about at least 55% elongation at yield (according to ASTM D 638); With the extremely about 1450psi (10MPa) of about 145psi (1MPa), more approximately 200psi (1.4MPa) is to about 1000psi (6.9MPa), and more about again 290psi (2MPa) is to the yield tensile strength (according to ASTMD 638) of 725psi (5MPa).This class material desirably shows less than about 85 Shore A, preferably less than about 80 Shore A, is more preferably less than the hardness (according to ASTM D-2240) of about 75 Shore A; With less than about 100MPa, preferably less than about 60MPa, be more preferably less than the modulus in flexure (according to ASTM D-790A) of about 44MPa (for example about 20 to 35MPa).The specific examples of suitable polypropylene-ethylene copolymer can be run after fame available from The Dow ChemicalCompany with VERSIFY (for example VERSIFY DE4300.01).
In a specific examples according to this instruction, second polyolefine is compatible with the first polyolefinic elastomeric component.Correspondingly, the polyolefine of the elastomeric component of first material and second material forms single-phase.
Can recognize that second material can be regarded as masterbatch effectively, or in specific examples, be regarded as " enriched material ".Therefore, from another viewpoint, the amount of filler in the enriched material (for example talcum) is usually greater than about 40 weight % of this enriched material, as enriched material about 45 to about 80 weight %, about more especially 60 to about 75 weight %.For example, select material separately amount so that filler in final material with less than about 40 weight %, more special in about 30 weight %, the more special again amount less than about 20 weight % exists.More specifically, overall filler content (for example, the filler for substantially being made of talcum is talc content) be final material about 2 to about 25 weight % (for example, final material about 5 to about 20 weight %, or even more particularly be final material about 8 to about 15 weight %).For example, the typical talc contents in the final material can have as about 5.5 weight %, about 8 weight %, about 10 weight %, about 12 weight %, about 15 weight % or even the value of about 18 weight %.In addition, if need one or more to plant additive in the final material, this class additive (comprising for example tinting material) can be included in this enriched material.
In one embodiment of the invention, can realize the talcum concentration of about 20 weight % (for example maximum about 15 weight %) at most in final material, wherein talcum does not show remarkably influenced to the contraction or the impact properties of final material.This class material desirably is ductile down at low temperature (for example about-30 ℃ or approximately-40 ℃).
In one approach, the particle of this second material can by mineral filler or micronization be polymer-coated or the part coating.This coating can alleviate the adhesion between the masterbatch particle.
Polyolefine used in first material and/or second material can comprise additional polyolefine, as propylene-ethylene copolymers (can modified rubber).The example of the suitable material that comprises polyolefine or substantially be made of polyolefine can be run after fame available from TheDow Chemical Company with C705-44NA or C715-12NHP.Other specific examples of the polymkeric substance that can use according to this instruction comprises those disclosed in WO 03/040201 A1, open U. S. application No.2003-0204017 and the U.S. Patent No. 6,525,157, and all these is incorporated herein by this reference.The polymkeric substance made from metalloscene catalyst also can be used in first material and/or second material.Can comprise this base polymer equally as the 3rd or other material beyond first and second materials.
Recognize, material is defined as " first " and " second " is for convenience's sake.Unless indicate, the use of these terms should not be regarded as getting rid of other material.Should not be regarded as showing that needs use any concrete order of procedure of processing yet.Except that above-mentioned first and second materials, can use other composition, include but not limited to disclosed in the industry composition, as one or more fillers, toughener, photostabilizer, tinting material, fire retardant, thermo-stabilizer, nucleator or analogue.
First, second with optional other material in two or more be considered to can be used as into cover material and supply together, for example in one or more suitable containers.This class becomes cover material and each constituent materials thereof therefore within the scope of the invention.
The goods that use the present invention to make comprise the filler grain that is present at first in the masterbatch.These filler grains can be stayed after blend in the polymkeric substance of masterbatch, and they can be dispersed in first polyolefine, or this combination takes place.In one embodiment of the invention, the initial major part that exists in second material (masterbatch) (for example about at least 50%, or more preferably about at least 75%) filler grain is stayed in first polyolefine after the melt blended material curing schedule finishes.
The material that is produced by the instruction of this paper has any combination of at least two kinds of (more special at least 3,4 kind or all) following character; That is, density about 0.85 is to about 1.25 gram/cubic centimetres, and about more especially 0.88 to about 1.10, and more about more especially 0.89 to about 1.06; Modulus in flexure is about 600 to about 2500MPa, and about more especially 700 to about 1700MPa, and about more especially 800 to about 1300MPa again; Tensile strength (under surrender) is 8MPa at least approximately, more special at least approximately 12MPa, more special more at least approximately 16MPa; Destruction in the ductility pattern (for example, multiaxis drop-dart impact test (Instrumented Dart Impact)) is about 60% greater than sample, about 100% (under-40 ℃ ,-30 ℃ or-20 ℃) of more special sample; Or average shrinkage (for example, mould direction or transverse mold are shunk (at 23 ℃ down after 1 or 24 hour, or 80 ℃ of post shrinkage after following 30 minutes, or both) less than about 1.4%, and be more special in about 1.1, more special in again about 1.0%.
More specifically, the material that is produced by the instruction of this paper has following any combination: the destruction in the ductility pattern (for example, multiaxis drop-dart impact test (Instrumented Dart Impact)) greater than about 60% of sample, about more especially 100% (under-40 ℃ ,-30 ℃ or-20 ℃) and notched Izod impact strength (under-20 ℃) be 15J/m at least approximately, more special at least approximately 20J/m, more special again 30J/m at least; With optional at least one following character: promptly density about 0.85 is to about 1.25, about more especially 0.88 to about 1.10 gram/cubic centimetres, and about more especially 0.89 to about 1.06 gram/cubic centimetres again; Modulus in flexure is about 600 to about 2500MPa, and about more especially 700 to about 1700MPa, and more special again 800 to about 1300MPa, approximately; Tensile strength (under surrender) is 8MPa at least approximately, more special at least approximately 12MPa, more special more at least approximately 16MPa; Or randomly, shrink less than 1.4%, more special in about 1.1%, more special again less than 1.0%.
Unless indicate separately, " melt flow rate (MFR) " measured by ISO 1133 working conditions M, 2.16 kilograms of its 230 ℃ of test temperature of regulation and load.This test conditions is usually used in polypropylene, comprises impact polypropylene.These values are known as " melt flow rate (MFR) " or " MFR ".Unless indicate separately, " melt index " measured by ISO 1133 working conditions D, 2.16 kilograms of its 190 ℃ of test temperature of regulation and load.This test conditions is usually used in polyethylene, comprises high density polyethylene(HDPE), new LDPE (film grade), LLDPE, very low density polyethylene and polyolefin plastomers.The measurement that these values are carried out is known as " melt index " or " MI ".Multiaxis or instrument (Instrumented) dart impact (IDI) energy measurement is according to ASTM D3763.For illustrative purpose, multiaxis drop-dart impact test (Instrumented Dart Impact) uses the 20001b ergometer to carry out on MTS 810 high-speed equipment.All samples are roughly 4 inches disk of about 0.125 inch thick diameter.Use about 13 millimeters tips to impact disk with about 6.7 meter per seconds.Screw-clamped is used for 0.5 inch in the outside, stays about 3 " pilot region.Ductile failure (this paper get the bid work " D ") stays the clean and tidy hole of passing the parts center, and wherein plastics are rushed out this hole, and naked eyes are not seen the crackle that radially extends outward.On 10 samples, repeat this test to obtain ductile failure per-cent.
Density measurement is according to ISO 1183 (method A).Notch shock beasurement base ISO 180 (method 1A).Percent crvstallinity is measured by dsc according to ASTM D3417.The milligram level sample of polymkeric substance is sealed in the aluminium DSC dish.Sample is packed in the DSC pond of 25 cubic centimetres of nitrogen purgings of per minute, and be cooled to-100 ℃.By being heated to 225 ℃ with 10 ℃/minute, set up the standard thermal history of sample.Then with sample cooling (10 ℃/minute) to-100 ℃ and with 10 ℃ of/minute reheat to 225 ℃.Record is to melting heat (Δ H that the second time, scanning arrived
Observe).Observed melting heat is associated with degree of crystallinity weight percent based on polypropylene specimen weight by following formula:
Wherein as B.Wunderlich, Macromolecular Physics, the 3rd volume, Crystal Melting, Academic Press, New York, the melting heat of the isotactic polyprophlene of report is 165 joule/gram polymkeric substance in 1980, the 48 pages.
Use the Rheometrics dynamic thermomechanical analysis apparatus by the pressing mold elastomer sample and heat up and measure second-order transition temperature (T
g).Second-order transition temperature is meant the temperature that is in tan delta peak.Under liquid nitrogen environment, carry out solid-state test with dynamic mode with the torsion anchor clamps.Use 3 ℃/minute temperature rise rate, frequency 1 radian per second, and initial strain is 0.1%.The running sample size has 45.0 mm lengths, 12.6 millimeters width and 3.2 millimeters thickness.
Unless indicate separately, modulus in flexure is measured by ISO 178.Tensile strength (under surrender) is measured by ISO 527-1/2.Shrinking percentage uses 150mm x 150mm x3mm plate to measure by ISO294.Brookfield viscosity is measured by ISO2555.
With reference to Fig. 1, the material that is produced by this instruction has the many rubber particles that are dispersed in the polyolefin matrix usually especially.The volume weighting mean diameter of particle is about 0.5 to about 5 microns, is more particularly about 1 to about 3 microns.Filler is considered to be distributed in the whole material, it is present in the matrix, in the rubber particles, between matrix and the rubber particles at the interface or its any combination.Further imagine, the rubber particles of about at least 20 volume % (more special about at least 35 volume %) has the diameter of about 1 to 3 micron (for example, about 1.5 to about 2.7 microns).Also imagined lamellar morphologies.
The transmission electron microscope (TEM) that atomic force microscope (AFM) or accompanying image are analyzed can be used for rubber domain size analysis.For example, AFM can be used for producing rubber aspect graph picture, and with the sampling of injection molding bar, streamwise is observed this core.For example, can use cryoultramicrotome (for example Leica Ultracut S/FCS) to take a sample being lower than under the temperature of glass transition temperature of polymer (for example-100 ℃).Afm image can use Tapping Mode
TM(Veeco Instruments, Inc., Santa Barbara, the trade mark of CA) obtains, and wherein cantilever vibrates with resonant frequency, and feedback control is regulated the constant amplitude that knocks.Use Veeco InstrumentsNanoscope software version 5.12b46 working diagram picture.Can use Leica Qwin software to carry out image analysis to obtain mean particle size and size-grade distribution.This software does not use the plane section correction of size-grade distribution.Can use this correction, and draw bigger size-grade distribution.
Goods of the present invention can be used for many purposes.Comprising the purposes of using polyolefine material, particularly TPO.For example, the material of making according to the instruction of this paper can be used as inside or external component attractively in carrier vehicle, as collision bumper, panel board, extraneous adornment, grid, side skirt, spoiler, gas dam, covering, interior trim panel, kneepad, dashboard, handle or analogue.These goods can also be made of the material according to this paper instruction substantially in moulding.They also can be the parts of assembly.The moulded products of making according to this paper instruction can for example be laminated on another structure, for example by welding, bonding, fastening piece or their any combination.These goods also can be the parts of the assembly of Overmolded or coinjection moulding.
The example of the adhesive composition that this paper is suitable for includes but not limited to, cyanoacrylate, (methyl) acrylic acid or the like, urethane, organosilicon, Resins, epoxy or analogue.A kind of attractive especially tackiness agent comprises as United States Patent(USP) Nos. 6,710,145; 6,713,579; 6,713,578; 6,730,759; 6,949,603; 6,806,330; With disclosed organo-borane/amine complex among open U. S. application Nos.2005-0004332 and the 2005-0137370; All these is quoted hereby and incorporates this paper into.
These goods also can be handled to improve its performance in secondary operation suitably.For example, but be not limited to, they can be coated with or otherwise surface treatment.For example, in one embodiment, body surfaces can be chosen wantonly before joining on another main body through pre-treatment.This optionally treating can comprise cleaning and degrease, plasma coating, Corona discharge Treatment, be coated with, uses adhesive coated or their any combination with another surface preparation.In one embodiment, main body can be as U.S. Patent No. 5,298,587; U.S. Patent No. 5,320,875; U.S. Patent No. 5,433,786 and U.S. Patent No. 5,494, carry out carbon-silicon dioxide base plasma deposition coating described in 712, all these is incorporated herein by this reference.Also can use other surface treatment, as the open in the industry Surface Treatment with Plasma of carrying out of instructing in the foundation U.S. Patent No. 5,837,958 (being incorporated herein by this reference).Also can use in-mold decoration.
The following example illustration all respects of the present invention.Institute's indicating value is approximation and should not be regarded as restriction of the present invention.As specification sheets in the whole text disclosed, the change of machined parameters is possible.In addition, shown in the result also may change (for example, shown in numerical value+/-10%, or even higher).
Embodiment
Table 1 is listed some polyolefine that can be used in second material with the filler compounding.AffinityGA1900 and Affinity GA1950 are the examples of available polyolefin plastomers.Can use other analogous material, for example can use density about 0.87 and have 8,000 to 17,000cps passes through the low viscous ethylene-octene plastomer that brookfield viscosity records under 177 ℃.The melt index of Affinity GA1900 and Affinity GA1950 was respectively 1000 and 500 grams/10 minutes (using ISO to record for 1133 condition D:190 ℃/2.16 kilograms).VersifyDE4300.01 is the research and development elastomerics of Dow Plastics manufacturing and is polypropylene-ethylene copolymer.Versify DE4300.01 has about 25 typical melt flow rate.
The masterbatch samples that contains talcum and Affinity GA1900 on the ZSK-25 twin screw extruder with the screw speed manufacturing of 200 shown in the table 2 to 450rpm.The talcum concentration of these samples is 40 weight % to 80 weight %.Other masterbatch samples are listed in the table 3, wherein AffinityGA1900 or Versify DE4300.01 and talcum compounding.
A kind of polyolefine that can be used as first material is an impact polypropylene.Table 4 is listed can be available from five kinds of exemplary impact polypropylenes of DowPlastics, DC7003, XUR-258, D143.00 research and development TPO, C705-44NA and C715-12NHP.These polypropylene all contain with the corresponding high rigidity of homopolymer polypropylene mutually and the soft phase corresponding with elastomeric ethylene copolymers.
Impact polypropylene is added the hopper of injection moulding machine with MB8 or MB9.Before adding injection moulding machine, with impact polypropylene and masterbatch dry blended by hand.The composition of these samples is listed in the table 5.Control sample 1 only contains polypropylene DC7003.Embodiment 2,3 and 4 contains 6%, 8% and 10% MB8 respectively and contains 94%, 92% and 90% polypropylene DC7003 respectively.Embodiment 5 contains 8% MB9 and 92% polypropylene DC7003.These samples all prepared under that impact polypropylene and masterbatch is the not melt blended situation before adding injection moulding machine.The machine that injection molding is used is the Demag/Ergotech 80-200 with 25 mm dia screw rods and about 20 length-to-diameter ratios (L/D).Screw rod is to be used for the master screw of impact polypropylene molding and not have mixing section.The compression ratio of screw rod is 2 to 3.Use is used for 3 millimeters plates or is used to stretch and the plug-in unit moulded specimen of crooked strip.This injection moulding machine and use comprise as the processing condition of other machine of the method for other local instruction of this paper:
Barrel zone temperature (from the nozzle to the opening for feed)
190-230 ℃ (for example 210)
190-230 ℃ (for example 210)
170-210 ℃ (for example 190)
150-190 ℃ (for example 170)
40-95 ℃ (for example 70)
Die temperature: 35-50 ℃/35-50 ℃ (for example 40 ℃/40 ℃)
Dosing speed: 150-190rpm (for example 170rpm)
Back pressure: 40-100 crust (for example 70 crust)
Dosing stroke: 70-80 millimeter (for example 74.5 millimeters)
Screw rod retreats: 73-83 millimeter (for example 77.5 millimeters) (about 3 millimeters decompression)
Overturn point: 8-12 millimeter (for example 10 millimeters)
Keep-up pressure: for tensile bar, 450-550 crust (for example 491 crust)
For 3 millimeters plates, 300-400 crust (for example 350 crust)
Hold-time: 30-50 second (for example 40 seconds)
Injection speed: 25-50 mm/second (for example 35 mm/second)
Cooling time: 10-20 second (for example 13 seconds)
Total cycle time+/-60 second (according to iso standard)
Control sample C6 prepares by injection molding XUR-258 polypropylene only.Embodiment 7-16 is by preparing with MB4 or MB5 according to the concentration injection molding polypropylene XUR-258 shown in the table 6.Polypropylene XUR-258 and MB4 or MB5 did not have melt blended before the hopper that adds injection moulding machine.
The AFM microgram of embodiment 4 is presented among Fig. 1.These micrograms show that this external phase is that what this was softer comprises that mutually they seem compatible by the elastomer polymer of impact polypropylene and Affinity GA1900 generation than inflexible polypropylene and softer discrete particle mutually (dark particle).In this AFM microgram, also can observe light talcum particle.The average score granularity of soft particle (average fraction particle size) is about 1.65 microns.This constitutes about 28% of total material mutually.
The AFM microgram of Fig. 1 also shows, behind material injection molding, the polypropylene that most of talcum particle may be stayed injection-molded parts mutually in.
As mentioned above, desirably, method of the present invention be not contained in substantially before the blend step with first, second and any the 3rd or other material be compounded in together step, particularly comprise the compounding step of the melt blended step of material.Recognize, be lower than doing of material melting point by use and mix step, still meet this requirement.For example, can before screw rod that starting material are incorporated herein and machine barrel assembly, the material pill be done mixed (for example by the agitating vane in the hopper).Can choose wantonly and use suitable feeder, as gravity-feeder (as described herein).
As can be seen, the instruction of this paper can make show with the current material of (for example before the hopper of introducing injection moulding machine) compounding before introducing shaped device quite or the molded thermoplastic goods of better properties feature.Advantageously, this material is processed to compare the resulting product with minimized substantially thermal history with the goods made from the blend of compounding in advance.
For any given purposes, although a certain feature of the present invention may only be described in one of exemplary, this feature can combine with one or more further features of other embodiment.From above also recognizing, the manufacturing of the unique texture of this paper and operation thereof also constitute method of the present invention.
Unless indicate separately, the size of various embodiments as herein described and geometric configuration are not to limit the present invention, and other size or geometric configuration are possible.A plurality of structure units or step can provide by single integrated morphology or step.Perhaps, single integrated morphology step can be divided into independently a plurality of parts or step.But, also function can be integrated in single parts or the step.In addition, the open of " a kind of " or " one " key element or step is not to get rid of other key element or step.
" approximately " or " roughly " of using with scope is applicable to two end values of this scope.Therefore, " about 20 to 30 " are intended to comprise " about 20 to about 30 ", comprise specified endpoint at least.
It being understood that above-mentioned explanation is exemplary and nonrestrictive.Those skilled in the art can be provided after reading above-mentioned explanation by many embodiments and the many purposes except that the embodiment that is provided.Therefore scope of the present invention should not determine with reference to above-mentioned explanation, but should determine with reference to the full breadth of the counterpart of claims and this class claim.All articles and reference comprise that patent application and disclosed disclosure are incorporated herein by this reference for various purposes.Omission to any aspect of theme disclosed herein in the following claim is not to abandon this theme, should not be considered to the part that the inventor is not considered as this class theme disclosed theme of the present invention yet.
Claims (27)
1, a kind of method of making moulded products comprises the following steps:
A) provide second material that comprises first polyolefinic first material and comprise following mixtures of material with the separate material form:
(i) account at least a fibrous mineral filler of about 45 to the 85 weight % of total mixture; With
(ii) account for about 15 to the 55 weight % of total mixture have according to ISO 1133 (condition D) record under 190 ℃/2.16 kilograms greater than/10 minutes at least the second polyolefine of melt index of about 150 grams;
B) when material is under the elevated temperature, first and second materials are applied shearing force so that the material blend is formed melt blended material;
C) with this melt blended material moulding; With
D) this melt blended material is solidified, wherein this method is not contained in before the blend step step that first and second materials is compounded in together substantially.
2, method according to claim 1, wherein first polyolefine of first material comprises TPO.
3, method according to claim 2, wherein this method is not contained in substantially before the blend step first, second and any optional other material is compounded in together step.
4, according to each described method of claim 1 to 3, it further comprises provides colour batch to realize the step of required color in the gained moulded products.
5, according to each described method of claim 1 to 4, its further comprise provide again grind in case with the step of at least the first and second material blend.
6, according to each described method of claim 1 to 5, wherein the step with the melt blended material moulding comprises melt blended material injection molding in mold cavity.
7, according to each described method of claim 1 to 6, wherein the TPO of first material comprises the polypropylene impact copolymer with following feature: less than/10 minutes (ISO 1133 condition M of about 70 grams, 230 ℃, 2.16 melt flow rate (MFR) kilogram), contain ethene greater than about 8 weight % (by the weight of first material), have degree of crystallinity greater than about 40%, or their any combination.
8, according to each described method of claim 1 to 7, the step that wherein provides comprises first and second materials dried mixed.
9, according to each described method of claim 1 to 8, wherein at least the first and second materials provide with the pill form.
10, method according to claim 9, the first material pill and the second material pill of wherein about at least 50 weight % have essentially identical volume.
11, according to each described method of claim 1 to 10, it further comprises additive and first material and second material mixing that is selected from thermo-stabilizer, ultra-violet stabilizer, releasing agent, nucleator, lubricant, surface slip agent, tinting material or its any combination with at least a.
12, according to each described method of claim 1 to 11, wherein the fibrous mineral filler is a talcum.
13, according to each described method of claim 1 to 12, wherein the fibrous mineral filler exists with the amount of about 70 weight % of total mixture.
14, according to each described method of claim 1 to 13, wherein second polyolefine comprises ethylene-octene copolymer.
15, according to each described method of claim 1 to 14, wherein first polyolefine comprises the ethene greater than about 8 weight % (by the weight of first material).
16, according to each described method of claim 1 to 15, wherein the steatitic median particle diameter is less than about 3 microns.
17, according to each described method of claim 1 to 16, wherein the average-volume of the particle of second material is greater than the average-volume of the granularity of first material.
18, according to each described method of claim 1 to 17, wherein second polyolefine is compatible with the first polyolefinic elastomeric component.
19, according to each described method of claim 1 to 18, wherein the particle of second material is by mineral filler or micronization is polymer-coated or part coating.
20, according to each described method of claim 1 to 19, wherein the shrinking percentage of injection-molded parts is less than about 1.4%.
21, according to each described method of claim 1 to 20, wherein first polyolefine comprises the TPO that is selected from reactor TPO, controlled rheology TPO and combination thereof.
22, according to each described method of claim 1 to 21, wherein the initial most of filler grain that exists is stayed in first polyolefine after the melt blended material curing schedule is finished in second material.
23, a kind of one-tenth cover material that is used for each described method of claim 1 to 22, wherein this becomes cover material comprising in the packing separately:
(i) first polyolefine;
(ii) at least a fibrous mineral filler; With
(iii) the melt index under 190 ℃/2.16 kilograms that records according to ISO 1133 (condition D) restrains/10 minutes second polyolefine greater than about 150.
24, one-tenth cover material according to claim 23, wherein first polyolefine comprises the ethene greater than about 8 weight % (by the weight of first material); Wherein mineral filler comprises talcum, and wherein second polyolefine comprises ethylene-octene copolymer.
25, according to claim 23 or 24 described one-tenth cover materials, it is further comprising the polyolefine different with first and second polyolefine in the packing separately.
26, a kind of goods, it is made according to each described method of claim 1 to 25.
27, a kind of purposes, it is the purposes according to the described goods of claim 26.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US80617906P | 2006-06-29 | 2006-06-29 | |
| US60/806,179 | 2006-06-29 | ||
| PCT/US2007/071902 WO2008002841A2 (en) | 2006-06-29 | 2007-06-22 | Thermoplastic articles and processes for making the same using an improved masterbatch |
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| CA (1) | CA2656615C (en) |
| MX (1) | MX2008016342A (en) |
| RU (1) | RU2009102825A (en) |
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| CN103804741A (en) * | 2014-01-10 | 2014-05-21 | 芜湖新磊塑胶科技有限公司 | Ceramic sculpture material as well as preparation method and application thereof |
| CN104395395A (en) * | 2012-04-12 | 2015-03-04 | 陶氏环球技术有限责任公司 | Polyolefin blend composition and articles made therefrom |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104395395A (en) * | 2012-04-12 | 2015-03-04 | 陶氏环球技术有限责任公司 | Polyolefin blend composition and articles made therefrom |
| CN104395395B (en) * | 2012-04-12 | 2016-10-12 | 陶氏环球技术有限责任公司 | Polyolefin blend compositions and goods prepared therefrom |
| CN103804741A (en) * | 2014-01-10 | 2014-05-21 | 芜湖新磊塑胶科技有限公司 | Ceramic sculpture material as well as preparation method and application thereof |
| CN103804741B (en) * | 2014-01-10 | 2016-08-17 | 芜湖新磊塑胶科技有限公司 | Porcelain carving material and its preparation method and application |
Also Published As
| Publication number | Publication date |
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| CA2656615A1 (en) | 2008-01-03 |
| ZA200810228B (en) | 2010-03-31 |
| BRPI0713204A8 (en) | 2017-12-12 |
| US20100216931A1 (en) | 2010-08-26 |
| CA2656615C (en) | 2012-07-24 |
| US7858688B2 (en) | 2010-12-28 |
| KR20090024196A (en) | 2009-03-06 |
| WO2008002841A2 (en) | 2008-01-03 |
| KR101052151B1 (en) | 2011-07-26 |
| WO2008002841A3 (en) | 2008-02-21 |
| MX2008016342A (en) | 2009-01-19 |
| US20080058455A1 (en) | 2008-03-06 |
| US7732521B2 (en) | 2010-06-08 |
| BRPI0713204A2 (en) | 2012-04-03 |
| JP5562029B2 (en) | 2014-07-30 |
| CN101490164B (en) | 2012-11-21 |
| EP2041221B1 (en) | 2014-06-04 |
| RU2009102825A (en) | 2010-08-10 |
| WO2008002841B1 (en) | 2008-04-03 |
| EP2041221A2 (en) | 2009-04-01 |
| JP2009542475A (en) | 2009-12-03 |
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